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The electrocatalytic CO2 reduction (eCO2R) reaction powered by renewable electricity holds promise for the sustainable production of multi-carbon chemicals and fuels. On Cu-based catalysts, ethylene and ethanol (C2) have been produced in appreciable amounts. C3 products (mostly terminal oxygenates) have limited yields, whereas propylene is puzzlingly absent. Herein, we devise a divide-and-conquer strategy to explain the formation of the C3-backbone and elucidate the mechanism responsible for the observed selectivity by combining network graphs, density functional theory, and experiments to prune the network and benchmark the identified path. Our approach concludes that the most frequently reported products, propionaldehyde and 1-propanol, originate from the coupling of CH2CH with C(H)O. While propylene and 1-propanol share common intermediates, the former is barely produced due to the unfavourable formation of allyl alkoxy (CH2CHCH2O), whose crucial nature was confirmed experimentally. This work paves the way for tailoring selective routes towards C3 products via eCO2R., Catalysis Science & Technology, 12 (2), ISSN:2044-4753, ISSN:2044-4761

A plethora of metal promoters have been applied to enhance the performance of In2O3 in CO2 hydrogenation to methanol, a prospective energy carrier. However, the lack of systematic catalyst preparation and evaluation precludes a direct comparison of their speciation and promotional effects, and consequently, the design of an optimal system. Herein, flame spray pyrolysis (FSP) is employed as a standardized synthesis method to introduce nine metal promoters (0.5 wt.%) into In2O3. Methanol productivity generally increased on M-In2O3 with selectivity following Pd approximate to Pt > Rh approximate to Ru approximate to Ir > Ni approximate to Co > Ag approximate to In2O3 > Au. In-depth characterization, kinetic analyses, and theoretical calculations reveal a range of metal-dependent speciation which dictate catalyst architecture and degree of promotion. Atomically-dispersed promoters (Pd, Pt, Rh, Ru, and Ir) grant the highest improvement in performance, particularly Pd and Pt, which markedly promote hydrogen activation while hindering undesired CO formation. In contrast, metals in clustered (Ni and Co) and nanoparticle (Ag and Au) forms display moderate and no promotion, respectively. This study provides an atomic-level understanding of In2O3 promotion based on a unified protocol, and highlights the potential of FSP to engineer complex catalytic systems toward more efficient energy transformations., Advanced Energy Materials, 12 (14)

CO2 electroreduction (CO2RR) is a sustainable alternative for producing fuels and chemicals. Metal cations in the electrolyte have a strong impact on the reaction, but mainly alkali species have been studied in detail. In this work, we elucidate how multivalent cations (Li+, Cs+, Be2+, Mg2+, Ca2+, Ba2+, Al3+, Nd3+, and Ce3+) affect CO2RR and the competing hydrogen evolution by studying these reactions on polycrystalline gold at pH = 3. We observe that cations have no effect on proton reduction at low overpotentials, but at alkaline surface pH acidic cations undergo hydrolysis, generating a second proton reduction regime. The activity and onset for the water reduction reaction correlate with cation acidity, with weakly hydrated trivalent species leading to the highest activity. Acidic cations only favor CO2RR at low overpotentials and in acidic media. At high overpotentials, the activity for CO increases in the order Ca2+ < Li+ < Ba2+ < Cs+. To favor this reaction there must be an interplay between cation stabilization of the *CO2– intermediate, cation accumulation at the outer Helmholtz plane (OHP), and activity for water reduction. Ab initio molecular dynamics simulations with explicit electric field show that nonacidic cations show lower repulsion at the interface, accumulating more at the OHP, thus triggering local promoting effects. Water dissociation kinetics is increasingly promoted by strongly acidic cations (Nd3+, Al3+), in agreement with experimental evidence. Cs+, Ba2+, and Nd3+ coordinate to adsorbed CO2 steadily; thus they enable *CO2– stabilization and barrierless protonation to COOH and further reduction products.

CO2 electroreduction (CO2RR) is a sustainable alternative for producing fuels and chemicals. Metal cations in the electrolyte have a strong impact on the reaction, but mainly alkali species have been studied in detail. In this work, we elucidate how multivalent cations (Li+, Cs+, Be2+, Mg2+, Ca2+, Ba2+, Al3+, Nd3+, and Ce3+) affect CO2RR and the competing hydrogen evolution by studying these reactions on polycrystalline gold at pH = 3. We observe that cations have no effect on proton reduction at low overpotentials, but at alkaline surface pH acidic cations undergo hydrolysis, generating a second proton reduction regime. The activity and onset for the water reduction reaction correlate with cation acidity, with weakly hydrated trivalent species leading to the highest activity. Acidic cations only favor CO2RR at low overpotentials and in acidic media. At high overpotentials, the activity for CO increases in the order Ca2+ < Li+ < Ba2+ < Cs+. To favor this reaction there must be an interplay between cation stabilization of the *CO2– intermediate, cation accumulation at the outer Helmholtz plane (OHP), and activity for water reduction. Ab initio molecular dynamics simulations with explicit electric field show that nonacidic cations show lower repulsion at the interface, accumulating more at the OHP, thus triggering local promoting effects. Water dissociation kinetics is increasingly promoted by strongly acidic cations (Nd3+, Al3+), in agreement with experimental evidence. Cs+, Ba2+, and Nd3+ coordinate to adsorbed CO2 steadily; thus they enable *CO2– stabilization and barrierless protonation to COOH and further reduction products.

Nanostructuring metal catalysts has been demonstrated as an attractive strategy to enable selective hydrodehalogenation of CH2X2 (X = Cl, Br) to CH3X, but active phase size effects of promising metals and the role of the halogen are still poorly understood. Herein, the impact of these parameters on performance (activity, selectivity, and stability) is systematically assessed by employing a platform of N–doped carbon–supported metal nanostructures (Ir, Pt, Ru, and Ni), ranging from single atoms (SA) with defined coordination environment to nanoparticles (NP) of ca. 3.0 nm. Catalytic tests reveal that when compared to single atoms, highest reaction rates are attained over NP–based systems, which also exhibit improved stability ranking as Ir ≈ Pt > Ru ≫ Ni, independent of the halogen. The product distribution was markedly affected by the nanostructure and speciation of the active center as well as the dihalomethane type. Specifically, CH3Cl is the main reaction product over SA in hydrodechlorination, achieving an exceptional selectivity over Ir (up to 95%). In contrast, NP mainly generated CH4 or coke. Comparable patterns were observed in hydrodebromination, except over Ru, which exhibited an inverse structure–selectivity trend. Density Functional Theory simulations shed light on the speciation of the active phase and identified the adsorption and dissociation energies of CH2X2 and H2 as descriptors for catalytic reactivity. These findings elucidate hydrodehalogenation performance patterns, highlighting the impact of nanostructuring and the halogen type to advance future catalyst design., Journal of Catalysis, 404, ISSN:0021-9517, ISSN:1090-2694

Atomically dispersed precious metals on oxide supports have recently become increasingly interesting catalytic materials. Nonetheless, their non-trivial preparation and limited thermal and environmental stability constitutes an issue for their potential applications. Here we demonstrate that an oxygen plasma pre-treatment of the ceria (CeO

Background and Purpose: Mechanical thrombectomy (MT) is effective for acute ischemic stroke (AIS) in selected patients with large intracranial vessel occlusion. A minority of patients with AIS receive MT. We aimed to describe the reasons for excluding patients with AIS for MT. Methods: We evaluated patients with AIS in a prospective population-based multicenter registry (Codi Ictus Catalunya registry) that includes all stroke code activations from January to June 2018 in Catalonia, Spain. We analyzed the major reasons for not treating with MT. Results: Stroke code was activated in 3060 patients. Excluding 355 intracranial hemorrhages and 502 stroke mimics, resulted in 2203 patients with AIS (mean age 72.8±13.8 years; 44.6% were women). Of the patients with AIS, 405 (18.4%) were treated with MT. We analyzed the reasons for not treating with MT. The following reasons were considered not modifiable: absence of large intracranial vessel occlusion (922, 41.9%), transient ischemic attack (206, 9.4%), and more than one cause (124, 5.6%). The potentially modifiable reasons for not performing MT by changing selection criteria were as follows: an intracranial artery occlusion that was considered inaccessible or not indicated (48, 2.2%); clinical presentation that was considered too mild to be treated (222, 10.1%); neuroimaging criteria (129, 5.9%), age/prior modified Rankin Scale score/medical comorbidities (129, 5.9%), and therapeutic time window >8 hours (16, 0.7%). Conclusions: In our area, considering all potentially modifiable causes for not performing MT, the percentage of patients with AIS eligible for MT could increase from 18.4% to a maximum of 43.1%. The clinical benefit of this increase is still uncertain and should be confirmed in future trials. Criteria for stroke code activation must be considered for the generalizability of these results.

Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common parameter-dependent one-electron approaches, such as density functional theory (DFT) with a Hubbard correction, or hybrid functionals. As a response, we present the first benchmark of ab initio many-electron theory for electron transfer energies and lattice parameters under periodic boundary conditions. We show that the direct random phase approximation clearly outperforms all DFT variations. From this foundation, we, then, systematically improve even further. Periodic second-order Møller–Plesset perturbation theory meanwhile manages to recover standard hybrid functional values. Using these approaches to eliminate parameter bias allows for highly accurate benchmarks of strongly correlated materials, the reliable assessment of various density functionals, and functional fitting via machine-learning.

The search for new catalytic materials has relied on highly time- and human- resource-consuming procedures. The appearance of theoretical methods that employ density functional theory coupled to kinetic models has allowed the rational understanding of activity volcano plots and selectivity abrupt profiles that resemble cliffs. However, these methodologies present several drawbacks as the optimization is confined to a family of materials, typically metals, and not applied to the overall phase and compositional space, therefore the maximum activity might not be sufficient for practical applications. Volcanos emerge from the symmetry between the adsorption energies of different intermediates on the catalyst, and thus circumventing these dependencies is crucial to identify better catalytic materials. Here we present a revision of the advances in the field that indicate that complexity in the materials is key to identifying alternative paths and thus overcome the drawbacks of scaling relationships. The energies of the species in a given reaction network are linked by linear scaling relationships, limiting the design of catalysts with improved activity and selectivity. In this Perspective, Lopez and Perez-Ramirez discuss strategies to circumvent such scaling relationships.

Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb2+ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination.

The use of chiral organic ligands during nanoparticle synthesis is key to designing optically active materials for biological and catalytic applications. To understand such complex processes at the...

The product distribution in direct alkane functionalization by oxyhalogenation strongly depends on the halogen of choice. We demonstrate that the superior selectivity to olefins over an iron phosphate catalyst in oxychlorination is the consequence of a surface‐confined reaction. By contrast, in oxybromination alkane activation follows a gas‐phase radical‐chain mechanism and yields a mixture of alkyl bromide, cracking, and combustion products. Surface‐coverage analysis of the catalyst and identification of gas‐phase radicals in operando mode are correlated to the catalytic performance by a multi‐technique approach, which combines kinetic studies with advanced characterization techniques such as prompt‐gamma activation analysis and photoelectron photoion coincidence spectroscopy. Rationalization of gas‐phase and surface contributions by density functional theory reveals that the molecular level effects of chlorine are pivotal in determining the stark selectivity differences. These results provide strategies for unraveling detailed mechanisms within complex reaction networks.

Electrocatalytic properties of materials are governed by the electronic structure, stability, and reactivity of the surface layer which is exposed to the electrolyte. Over the years, different strategies have been developed to tailor electrocatalyst surfaces but also to reduce the cost of these materials, which is the bottleneck for any practical application. When a very thin metallic layer, intended to serve as an electrocatalyst, is placed over a substrate, its configuration is influenced by the structure of the substrate due to lattice mismatch, while the electronic structure is affected due to the strain and the electronic effects of the support. This results in altered bonding within the electrocatalyst layer and the modification of its electronic properties when compared to the pure phase. In this contribution, we address the possibilities of theoretical prediction of surface properties of atomically thin electrocatalyst films formed over different substrates, focusing on the metal side of the elect...

The frontiers between homogeneous and heterogeneous catalysis are progressively disappearing. The decoration of transition metal nanoparticles (NPs) with ligands, also known as surface modifiers or capping agents, primarily allows NP size control but dramatically impacts activity and selectivity in catalysis. Computational tools have shown their capability of providing insight at atomic level in both homogeneous and heterogeneous areas but, due to the complexity of these interfaces, the underlying reaction mechanisms are often not described and certainly not well understood. In this mini-review, we describe the main challenges in modelling and survey the most recent computational studies that emphasise the role of ligands in tuning catalytic performance. We focus on density functional theory (DFT) simulations of the interfaces between transition metals (ruthenium, palladium, platinum, gold) and organic ligands (NHC, amine, phosphine, thiol), surfactants, and ionic liquids. Revealing the reaction pathways that operate at this hidden interface between homogeneous and heterogeneous worlds will provide guiding rules to design new systems that circumvent linear scaling relationships and foster a unified theory of catalysis.

Optimization of metal–support interactions (MSIs) is at the core of heterogeneous catalyst design. For polar reactants, electrostatic interactions resulting from MSIs can facilitate their activation. In this work, a feasible in situ method has been employed to control the electrostatic properties at the interface of a noble-metal-free Cu/Co(OH)2 nanohybrid catalyst. On the Cu/Co(OH)2 interface, the positively charged copper enhances the polar molecule adsorption. By varying the metal/support ratio, a highly efficient catalytic activity for the methanolysis of ammonia borane (AB) with an initial turnover frequency (TOF) of 61.63 mol(H2) mol(catalyst)−1 min−1 and long-term stability at ambient temperature were observed. Theoretical analysis unravels the role of charge transfer in promoting the reactions and the metal/support ratio in manipulating the catalytic activity via tuning electrostatic interactions.

The catalytic activity of membranes produced with commercial unmodified reduced graphene oxide (rGO) was demonstrated for the first time in persulfate (PS) activation through experiments performed in continuous mode. Phenol (Ph; C-0 = 5 mg L-1) and venlafaxine (VFX; C-0 = 250 mu g L-1) were employed as model compounds. The influence of the main operation parameters was first investigated considering an operation period of 24 h. For a rGO membrane with an effective area of 2.1 cm(2) , contaminant removal is favored at lower flow rates (0.1 mL min(-1)) and higher catalyst loads (15 mg). Assays carried out under these conditions yielded average removals of 90 and 94% for Ph and VFX, respectively, corresponding to normalized removal rates in the range of 1.71-1.79 L m(-2) h(-1) mg(cat)(-1). Membrane stability tests were conducted in continuous mode for 1 week, allowing to observe a significant catalyst deactivation after 2-3 d of operation, although the catalytic activity could be recovered through simple thermal regeneration procedures. Batch mode oxidation tests employing powder rGO treated at different temperatures (500, 850 and 1000 degrees C) and materials characterization data allowed to conclude that a shift of the surface chemistry character from acidic to basic enhances the catalytic performance. Moreover, scavenging tests indicated that singlet oxygen (O-1(2)), apparently generated by nucleophilic attack of PS to C = O in pyrone-like functionalities, is the main oxidizing species in the rGO-PS system.

Nowadays, reaction mechanisms of photo-Fenton process with chelated iron are not yet clearly defined. In this study, five organic fertilizers were used as iron complexes to investigate the role of sunlight and oxygen in photo-Fenton at near neutral pH. UV absorbance and stability constant of each selected iron chelate is different, and this work demonstrates that these parameters affect the reaction mechanisms in SMX degradation. Irradiation experiments without H2O2 revealed that only EDDS-Fe and DTPA-Fe achieved SMX degradation, but different iron release. These results, together with soluble oxygen free experiments, allowed the proposal of complementary reaction mechanisms to those of the classical photo-Fenton. The proposed mechanisms start through the potential photoexcitation of the iron complex, followed by subsequent oxygen-mediated hydroxyl radical generation reactions that are different for EDDS-Fe and DTPA-Fe. Moreover, irradiation experiments using EDTA-Fe and HEDTA-Fe had negligible SMX degradation despite iron release was observed, evidencing the differences between iron chelates., The authors are grateful with the Ministry of Economy and Competitiveness (project CTQ2017-86466-R, MINECO/FEDER, UE), AGAUR-Generalitat de Catalunya (project 2017SGR-131) and Nuria López FPU research fellowship (FPU-16/02101) financed by Ministry of Science, Innovation and Universities.

The Fischer-Tropsch (FT) synthesis of fuels from CO and H2 lies at the heart of the successful and mature Gas-to-Liquid technology; however its reliance on fossil resources comes with the burden of an undesirable carbon footprint. In contrast, the electroreduction of CO2 (CO2RR) powered by renewable electricity has the potential to produce the same type of fuels, but in a carbon-neutral fashion. To date, only ethylene and ethanol are attainable at reasonable efficiencies and exclusively on copper. Herein, we report that the oxygenated compounds of nickel can selectively electroreduce CO2 to C1 – C6 hydrocarbons with significant yields (Faradaic efficiencies of C3+ up to 6.5%). While metallic Ni only produces hydrogen and methane under CO2RR and FT conditions respectively, we show that polarized nickel (Niδ+) sites facilitate ambient CO2RR via the FT mechanism. The catalysts yield multi-carbon molecules with an unprecedented chain growth probability values (α) up to 0.44, which matches many technical FT synthesis systems. We anticipate that the integration of the herein proposed electrochemical-FT scheme with fuel cells may provide at this seminal stage up to 7% energy efficiency for C3+ hydrocarbons, inaugurating a new era towards the defossilization of the chemical industry.

Controlling the precise atomic architecture of supported metals is central to optimizing their catalytic performance, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key process for vinyl chloride production. This opens the possibility of building on historically established activity correlations. In this study, we derived quantitative activity, selectivity and stability descriptors that account for the metal-dependent speciation and host effects observed in acetylene hydrochlorination. To achieve this, we generated a platform of Au, Pt, Ru, Ir, Rh and Pd single atoms and nanoparticles supported on different types of carbon and assessed their evolution during synthesis and under the relevant reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identified the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining catalyst selectivity with respect to coke formation. The stability of the different nanostructures is governed by the interplay between single atom-support interactions and chlorine affinity, promoting metal redispersion or agglomeration, respectively.

The electroreduction of CO

Sustainable electrocatalysis of the oxygen evolution reaction (OER) constitutes a major challenge for the realization of green fuels. Oxides based on Ni and Fe in alkaline media have been proposed to avoid using critical raw materials. However, their ill-defined structures under OER conditions make the identification of key descriptors difficult. Here, we have studied Fe−Ni−Zn spinel oxides, with a well-defined crystal structure, as a platform to obtain general understanding on the key contributions. The OER reaches maximum performance when: (i) Zn is present in the Spinel structure, (ii) very dense, equimolar 1 : 1 : 1 stoichiometry sites appear on the surface as they allow the formation of oxygen vacancies where Zn favors pushing the electronic density that is pulled by the octahedral Fe and tetrahedral Ni redox pair lowering the overpotential. Our work proves cooperative electronic effects on surface active sites as key to design optimum OER electrocatalysts., This work was funded by the European Union under the H2020 FET-PROACT A-LEAF project (Grant Agreement No. 732840). The authors thankfully acknowledge the computer resources at MareNostrum and the technical support provided by the Barcelona Supercomputing Center (QCM-2018-3-0012 Theoretical studies on catalysis optimization for an Artificial Leaf (A-LEAF)). ICN2 acknowledge funding from Generalitat de Catalunya 2017 SGR 327. ICN2 and UJI acknowledge funding from the Spanish MINECO coordinated project VALPEC (ENE2017-85087-C3). ICN2 is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706) and is funded by the CERCA Programme / Generalitat de Catalunya.

PRACE (Partnership for Advanced Computing in Europe), an international not-for-profit association that brings together the five largest European supercomputing centers and involves 26 European countries, has allocated more than half a billion core hours to computer simulations to fight the COVID-19 pandemic. Alongside experiments, these simulations are a pillar of research to assess the risks of different scenarios and investigate mitigation strategies. While the world deals with the subsequent waves of the pandemic, we present a reflection on the use of urgent supercomputing for global societal challenges and crisis management. Peer Reviewed "Article signat per 18 autors/es: Núria López, Luigi Del Debbio, Marc Baaden, Matej Praprotnik, Laura Grigori, Catarina Simões, Serge Bogaerts, Florian Berberich, Thomas Lippert, Janne Ignatius, Philippe Lavocat, Oriol Pineda, Maria Grazia Giuffreda, Sergi Girona, Dieter Kranzlmüller, Michael M. Resch, Gabriella Scipione, and Thomas Schulthess"

Severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) pandemic has challenged societies around the globe. Technologies based on ozone, a powerful oxidant, have been evaluated to inactivate this virus in aerosols and fomites. However, the high data diversity hinders the possibility of establishing a common ground for determining best practices for the use of these technologies. Furthermore, there is a lack of consensus regarding which are the main mechanisms of ozone virus inactivation. This critical review examined the most relevant information available regarding ozone application in gas-phase for different viruses inactivation (including recent publications dealing with SARS-CoV-2), and pointed towards envelope alteration as the main reaction pathway for enveloped viruses, such as is the case of SARS-CoV-2. It could also be concluded that gaseous ozone can be indeed an effective disinfectant, successfully inactivating viruses such us influenza A H1N1, MERS-CoV, SARS-CoV-1 or even SARS-CoV-2 in aerosols or fomites. In reviewed works, low ozone exposures, just around 0.1–0.4 mg L-1 min, achieve about 4 log10 of inactivation in aerosols, while exposures between 1 and 4 mg L-1 min may be needed to guarantee an inactivation of 3–4 log10 in different fomites. Although further studies are required, ozone is an effective candidate to be used against SARS-CoV-2 or other viruses in surfaces and indoor locations., Graphical Abstract ga1

Background The role of children in household transmission of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) remains unclear. We describe the epidemiological and clinical characteristics of children with coronavirus disease 2019 (COVID-19) in Catalonia, Spain, and investigate the household transmission dynamics. Methods A prospective, observational, multicenter study was performed during summer and school periods (1 July 2020–31 October 2020) to analyze epidemiological and clinical features and viral household transmission dynamics in COVID-19 patients aged Results The study included 1040 COVID-19 patients. Almost half (47.2%) were asymptomatic, 10.8% had comorbidities, and 2.6% required hospitalization. No deaths were reported. Viral transmission was common among household members (62.3%). More than 70% (756/1040) of pediatric cases were secondary to an adult, whereas 7.7% (80/1040) were index cases. The SAR was significantly lower in households with COVID-19 pediatric index cases during the school period relative to summer (P = .02) and compared to adults (P = .006). No individual or environmental risk factors associated with the SAR. Conclusions Children are unlikely to cause household COVID-19 clusters or be major drivers of the pandemic, even if attending school. Interventions aimed at children are expected to have a small impact on reducing SARS-CoV-2 transmission.

Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common parameter-dependent one-electron approaches, such as density functional theory (DFT) with a Hubbard correction, or hybrid functionals. As a response, we present the first benchmark of ab initio many-electron theory for electron transfer energies and lattice parameters under periodic boundary conditions. We show that the direct random phase approximation clearly outperforms all DFT variations. From this foundation, we, then, systematically improve even further. Periodic second-order M{\o}ller-Plesset perturbation theory meanwhile manages to recover standard hybrid functional values. Using these approaches to eliminate parameter bias allows for highly accurate benchmarks of strongly correlated materials, the reliable assessment of various density functionals, and functional fitting via machine-learning., Comment: 7 pages, 3 figures, 1 table

Five organic fertilizers (DTPA, EDDHA, HEDTA, EDTA and EDDS) were studied as iron sources for photo-Fenton process at natural pH to remove micropollutants (MPs) from wastewater for its reuse in irrigation. The results demonstrated that the stability constant of iron chelates is a key parameter for optimal micropollutants removal and it is linked to the structure of chelator. Mixtures of organic fertilizers were also tested to overcome excessive iron loose and to optimize MPs abatement kinetics. An improvement of photo-Fenton process occurred when using chelating mixtures. For instance, with 50 %EDDS + 50 %EDTA total removal of propranolol (PROP) was achieved at 30 min while EDTA needed up to 90 min of reaction and with EDDS total degradation was not achieved. In addition, the availability of dissolved iron of the mixture at the end of the treatment was 5.5 times higher than EDDS, increasing its suitability as reuse water for irrigation.

Metal promotion in heterogeneous catalysis requires nanoscale-precision architectures to attain maximized and durable benefits. Herein, we unravel the complex interplay between nanostructure and product selectivity of nickel-promoted In2O3 in CO2 hydrogenation to methanol through in-depth characterization, theoretical simulations, and kinetic analyses. Up to 10 wt.% nickel, InNi3 patches are formed on the oxide surface, which cannot activate CO2 but boost methanol production supplying neutral hydrogen species. Since protons and hydrides generated on In2O3 drive methanol synthesis rather than the reverse water-gas shift but radicals foster both reactions, nickel-lean catalysts featuring nanometric alloy layers provide a favorable balance between charged and neutral hydrogen species. For nickel contents >10 wt.%, extended InNi3 structures favor CO production and metallic nickel additionally present produces some methane. This study marks a step ahead towards green methanol synthesis and uncovers chemistry aspects of nickel that shall spark inspiration for other catalytic applications., Nature Communications, 12 (1), ISSN:2041-1723

Introduction: Clonal evolution drives cancer development due to the emergence and/or selection of proliferatively advantageous subclones. Its understanding may facilitate the design of anticipation-based management strategies. Richter transformation (RT) is a paradigmatic tumor evolution in which chronic lymphocytic leukemia (CLL), an indolent neoplasia of mature B-cells, transforms into a high-grade lymphoma, usually diffuse large B-cell lymphoma (DLBCL), conferring a dismal prognosis. The evolutionary trajectories of RT and its driving (epi)genomic mechanisms remain largely unknown. Aims: To reconstruct the evolutionary history of RT and to reveal the molecular processes underlying this transformation. Methods: We characterized the whole genome (WGS), epigenome (DNA methylation, H3K27ac, ATAC-seq), and transcriptome (RNA-seq), combined with single-cell DNA and RNA sequencing analyses, of 19 CLL patients developing RT before (n=3) or after treatment with chemoimmunotherapy (n=6) and targeted therapies (BCR or BCL2 inhibitors, n=10). We analyzed 54 longitudinal samples covering up to 19 years of disease course. Results: Our WGS analyses uncovered that RT is characterized by a remarkable structural complexity. We also identified a novel treatment-independent RT-specific mutational process, which we named SBS-RT. The genetic driver landscape of RT is a compendium of alterations in genes involved in cell cycle, MYC, and NF-κB pathways, frequently targeted in single catastrophic events including chromothripsis and chromoplexy. The WGS-based phylogenic reconstruction and single-cell DNA/RNA-seq analyses identified a very early diversification of CLL leading to emergence of RT-cells carrying specific genetic drivers and transcriptomic profiles of RT already at CLL diagnosis. These small subclones were dormant for 6-19 years until rapid expansion associated with the clinical transformation. While the DNA methylome kept track of the cell of origin and proliferative history of RT cells, their chromatin configuration and transcriptional program converged into the overexpression of cell cycle regulators, Toll-like receptors, MYC, MTORC1, and OXPHOS related transcripts, as well as downregulation of BCR pathway. This phenotypic shift was related to de novo activation of key transcription factors. In vitro experiments confirmed that RT cells have a 4-fold higher oxygen consumption at routine respiration and electron transfer system capacity compared to CLL. The resistance of RT to BCR inhibition is consistent with its high OXPHOS and low BCR signaling, which mimics de novo DLBCL-OXPHOS insensitive to BCR inhibition. This OXPHOShigh-BCRlow transcriptional axis of RT can be exploited therapeutically. Conclusions: These findings demonstrate the early seeding of subclones driving advanced stages of cancer evolution and uncover therapeutic targets for the, once expanded, lethal Richter transformation. Citation Format: Ferran Nadeu, Romina Royo, Ramon Massoni-Badosa, Beatriz Garcia-Torre, Martí Duran-Ferrer, Kevin J. Dawson, Marta Kulis, Ander Diaz-Navarro, Neus Villamor, Juan L. Melero, Vicente Chapaprieta, Ana Dueso-Barroso, Julio Delgado, Riccardo Moia, Sara Ruiz-Gil, Domenica Marchese, Núria Verdaguer-Dot, Mónica Romo, Maria Rozman, Gerard Frigola, Alfredo Rivas-Delgado, Tycho Baumann, Miguel Alcoceba, Marcos González, Fina Climent, Pau Abrisqueta, Josep Castellví, Francesc Bosch, Marta Aymerich, Anna Enjuanes, Sílvia Ruiz-Gaspà, Armando López-Guillermo, Pedro Jares, Sílvia Beà, Dolors Colomer, Núria López-Bigas, Josep LlGelpí, David Torrents, Peter J. Campbell, Ivo Gut, Pablo M. Garcia-Roves, Davide Rossi, Gianluca Gaidano, Xose S. Puente, Holger Heyn, Francesco Maura, José I. Martín-Subero, Elías Campo. Early seeding of Richter transformation in chronic lymphocytic leukemia [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2022; 2022 Apr 8-13. Philadelphia (PA): AACR; Cancer Res 2022;82(12_Suppl):Abstract nr 3795.